US5049602A - Costabilizers for molding compositions based on polymers of vinyl chloride - Google Patents
Costabilizers for molding compositions based on polymers of vinyl chloride Download PDFInfo
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- US5049602A US5049602A US07/589,803 US58980390A US5049602A US 5049602 A US5049602 A US 5049602A US 58980390 A US58980390 A US 58980390A US 5049602 A US5049602 A US 5049602A
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- 239000000203 mixture Substances 0.000 title claims abstract description 65
- 229920000642 polymer Polymers 0.000 title claims abstract description 26
- 238000000465 moulding Methods 0.000 title claims description 14
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title abstract description 6
- 239000003381 stabilizer Substances 0.000 claims abstract description 65
- 229920001577 copolymer Polymers 0.000 claims abstract description 12
- 238000009757 thermoplastic moulding Methods 0.000 claims abstract description 12
- 229920000765 poly(2-oxazolines) Polymers 0.000 claims abstract description 7
- 229920005862 polyol Polymers 0.000 claims abstract description 5
- 150000003077 polyols Chemical class 0.000 claims abstract description 5
- -1 phenylaminocarbonyl Chemical group 0.000 claims description 131
- 239000011701 zinc Substances 0.000 claims description 112
- 125000004432 carbon atom Chemical group C* 0.000 claims description 58
- 150000001875 compounds Chemical class 0.000 claims description 43
- 125000000217 alkyl group Chemical group 0.000 claims description 25
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 19
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 17
- 239000004800 polyvinyl chloride Substances 0.000 claims description 12
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 11
- 125000004122 cyclic group Chemical group 0.000 claims description 11
- 229910052725 zinc Inorganic materials 0.000 claims description 11
- 125000003118 aryl group Chemical group 0.000 claims description 10
- 239000011575 calcium Substances 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 8
- 239000000460 chlorine Substances 0.000 claims description 8
- 229910052801 chlorine Inorganic materials 0.000 claims description 8
- 229910052736 halogen Inorganic materials 0.000 claims description 8
- 150000002367 halogens Chemical class 0.000 claims description 8
- 125000002947 alkylene group Chemical group 0.000 claims description 7
- 150000002431 hydrogen Chemical group 0.000 claims description 7
- 150000002148 esters Chemical class 0.000 claims description 6
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 6
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 5
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- 125000002252 acyl group Chemical group 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 125000004450 alkenylene group Chemical group 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000004448 alkyl carbonyl group Chemical group 0.000 claims description 4
- 125000006356 alkylene carbonyl group Chemical group 0.000 claims description 4
- 125000005529 alkyleneoxy group Chemical group 0.000 claims description 4
- 125000006165 cyclic alkyl group Chemical class 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- 229910052793 cadmium Inorganic materials 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- FCSHMCFRCYZTRQ-UHFFFAOYSA-N N,N'-diphenylthiourea Chemical compound C=1C=CC=CC=1NC(=S)NC1=CC=CC=C1 FCSHMCFRCYZTRQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 235000013877 carbamide Nutrition 0.000 claims description 2
- 150000002475 indoles Chemical class 0.000 claims description 2
- 150000003217 pyrazoles Chemical class 0.000 claims description 2
- 150000003585 thioureas Chemical class 0.000 claims description 2
- 150000003672 ureas Chemical class 0.000 claims description 2
- 150000001912 cyanamides Chemical class 0.000 claims 1
- 150000002989 phenols Chemical class 0.000 claims 1
- 150000003752 zinc compounds Chemical class 0.000 abstract description 4
- 125000004925 dihydropyridyl group Chemical group N1(CC=CC=C1)* 0.000 abstract description 3
- 150000003233 pyrroles Chemical class 0.000 abstract description 3
- 230000000087 stabilizing effect Effects 0.000 abstract description 3
- 150000002918 oxazolines Chemical class 0.000 abstract description 2
- 238000009472 formulation Methods 0.000 description 27
- 230000008642 heat stress Effects 0.000 description 24
- 235000021355 Stearic acid Nutrition 0.000 description 11
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 11
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 11
- 239000008117 stearic acid Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 8
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 6
- 239000000194 fatty acid Substances 0.000 description 6
- 239000012170 montan wax Substances 0.000 description 6
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical class [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 5
- 101100412856 Mus musculus Rhod gene Proteins 0.000 description 4
- 101100242191 Tetraodon nigroviridis rho gene Proteins 0.000 description 4
- AGXUVMPSUKZYDT-UHFFFAOYSA-L barium(2+);octadecanoate Chemical compound [Ba+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AGXUVMPSUKZYDT-UHFFFAOYSA-L 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000005711 Benzoic acid Substances 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 235000010233 benzoic acid Nutrition 0.000 description 3
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 3
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000344 soap Substances 0.000 description 3
- LRQGFQDEQPZDQC-UHFFFAOYSA-N 1-Phenyl-1,3-eicosanedione Chemical compound CCCCCCCCCCCCCCCCCC(=O)CC(=O)C1=CC=CC=C1 LRQGFQDEQPZDQC-UHFFFAOYSA-N 0.000 description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- 229920009204 Methacrylate-butadiene-styrene Polymers 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical group CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 229910009378 Zn Ca Inorganic materials 0.000 description 2
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 229920006187 aquazol Polymers 0.000 description 2
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- VACHUYIREGFMSP-UHFFFAOYSA-N (+)-threo-9,10-Dihydroxy-octadecansaeure Natural products CCCCCCCCC(O)C(O)CCCCCCCC(O)=O VACHUYIREGFMSP-UHFFFAOYSA-N 0.000 description 1
- NMBZRXYPTRKTCN-UHFFFAOYSA-N (2,4-ditert-butylphenyl) didodecyl phosphite Chemical compound CCCCCCCCCCCCOP(OCCCCCCCCCCCC)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C NMBZRXYPTRKTCN-UHFFFAOYSA-N 0.000 description 1
- QIBOWVKBPQNSBZ-UHFFFAOYSA-N (2,6-ditert-butylphenyl) didodecyl phosphite Chemical compound CCCCCCCCCCCCOP(OCCCCCCCCCCCC)OC1=C(C(C)(C)C)C=CC=C1C(C)(C)C QIBOWVKBPQNSBZ-UHFFFAOYSA-N 0.000 description 1
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- JPFGKGZYCXLEGQ-UHFFFAOYSA-N 1-(4-methoxyphenyl)-5-methylpyrazole-4-carboxylic acid Chemical compound C1=CC(OC)=CC=C1N1C(C)=C(C(O)=O)C=N1 JPFGKGZYCXLEGQ-UHFFFAOYSA-N 0.000 description 1
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical group CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 1
- LUBJCRLGQSPQNN-UHFFFAOYSA-N 1-Phenylurea Chemical compound NC(=O)NC1=CC=CC=C1 LUBJCRLGQSPQNN-UHFFFAOYSA-N 0.000 description 1
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical group CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 1
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical group CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N 1-nonene Chemical group CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical group CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- GZQKJQLFIGBEIE-UHFFFAOYSA-N 2-[4-(4,5-dihydro-1,3-oxazol-2-yl)butyl]-4,5-dihydro-1,3-oxazole Chemical compound N=1CCOC=1CCCCC1=NCCO1 GZQKJQLFIGBEIE-UHFFFAOYSA-N 0.000 description 1
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- NYEZZYQZRQDLEH-UHFFFAOYSA-N 2-ethyl-4,5-dihydro-1,3-oxazole Chemical compound CCC1=NCCO1 NYEZZYQZRQDLEH-UHFFFAOYSA-N 0.000 description 1
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- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- OYYXZGFIZTYYRB-UHFFFAOYSA-N 2-octyldecanoic acid Chemical compound CCCCCCCCC(C(O)=O)CCCCCCCC OYYXZGFIZTYYRB-UHFFFAOYSA-N 0.000 description 1
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- FVEZUCIZWRDMSJ-UHFFFAOYSA-N 2-propan-2-yl-4,5-dihydro-1,3-oxazole Chemical compound CC(C)C1=NCCO1 FVEZUCIZWRDMSJ-UHFFFAOYSA-N 0.000 description 1
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical class CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 1
- FYYGCTQPBDNICZ-UHFFFAOYSA-N 2-tetradecyloctadecanoic acid Chemical compound CCCCCCCCCCCCCCCCC(C(O)=O)CCCCCCCCCCCCCC FYYGCTQPBDNICZ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 description 1
- FLZYQMOKBVFXJS-UHFFFAOYSA-N 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoic acid Chemical compound CC1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O FLZYQMOKBVFXJS-UHFFFAOYSA-N 0.000 description 1
- 125000004179 3-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(Cl)=C1[H] 0.000 description 1
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
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- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 1
- VACHUYIREGFMSP-SJORKVTESA-N 9,10-Dihydroxystearic acid Natural products CCCCCCCC[C@@H](O)[C@@H](O)CCCCCCCC(O)=O VACHUYIREGFMSP-SJORKVTESA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000004801 Chlorinated PVC Substances 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- 239000004908 Emulsion polymer Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
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- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
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- 125000000400 lauroyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 239000000314 lubricant Substances 0.000 description 1
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 1
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- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 1
- VUQUOGPMUUJORT-UHFFFAOYSA-N methyl 4-methylbenzenesulfonate Chemical compound COS(=O)(=O)C1=CC=C(C)C=C1 VUQUOGPMUUJORT-UHFFFAOYSA-N 0.000 description 1
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- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
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- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
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- 101150035983 str1 gene Proteins 0.000 description 1
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- TUNFSRHWOTWDNC-UHFFFAOYSA-N tetradecanoic acid Chemical class CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 1
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- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- KFUSEUYYWQURPO-OWOJBTEDSA-N trans-1,2-dichloroethene Chemical compound Cl\C=C\Cl KFUSEUYYWQURPO-OWOJBTEDSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- FICPQAZLPKLOLH-UHFFFAOYSA-N tricyclohexyl phosphite Chemical compound C1CCCCC1OP(OC1CCCCC1)OC1CCCCC1 FICPQAZLPKLOLH-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/02—Polyamines
Definitions
- chlorine-containing polymers are post-chlorinated PVC and chlorinated polyolefins, and also graft copolymers of PVC with ethylene-vinyl acetate (EVA), acrylonitrile-butadienestyrene (ABS) and methacrylate-butadiene-styrene (MBS).
- EVA ethylene-vinyl acetate
- ABS acrylonitrile-butadienestyrene
- MFS methacrylate-butadiene-styrene
- R 9 is methyl or phenyl
- R 10 is hydrogen, cyano, C 2 -C 19 -alkylcarbonyl, C 7 -C 10 -arylcarbonyl, phenylaminocarbonyl, m-hydroxyphenylaminocarbonyl, ⁇ -hydroxyethyl, or carboxyl esterified with a C 1 -C 18 -alcohol, C 5 -C 8 -cycloalkanol, C 5 -C 19 -aralkanol, C 2 -C 20 -alkanediol, C 4 -C 20 -thioalkanediol or pentaerythritol, and R 11 is methyl, phenyl or (C 1 -C 19 -alkoxy) methyl.
- VESTOLIT S 6058 100 parts by wt. of VESTOLIT S 6058
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Costabilizers which are composed of pyrroles and/or dihydropyridines and/or copolymers of oxazolines and bisoxazolines and/or polyols enhance the stabilizing effect of primary stabilizers such as polyoxazolines and zinc compounds in thermoplastic molding compositions, such as those based on polymers of vinyl chloride.
Description
1. Field of the Invention
The present invention relates to rigid or plasticized, stabilized thermoplastic molding compositions based on halogen-containing polymers, in particular polyvinyl chloride or polymers containing essentially vinyl chloride.
2. Discussion of the Background
It is known that chloride-containing polymers are readily degraded by the action of heat, for example during processing. This degradation leads to undesired discolorations and to an impairment of the mechanical properties. Consequently, this degradation is avoided by adding stabilizers to the polymers before processing. In the case of polyvinyl chloride and copolymers containing essentially vinyl chloride, particular use is made of organotin compounds, inorganic and organic lead salts, organic antimony compounds or combinations of cadmium carboxylates and barium carboxylates and also of a mixture of zinc soaps and polyoxazolines. These so-called primary stabilizers are frequently supplemented with costabilizers to improve their effectiveness. The modes of action of primary or costabilizers and their combined action (synergism) are described in the relevant literature, for example in the publication by L. I. Nass, "Heat Stabilizers", Kirk-Othmer Encyclopedia of Chemical Technology, volume 12, 3rd edition, page 225, published by John Wiley and Sons, 1980.
Essentially, these are costabilizers which improve the initial color and the ultimate stability of the chlorine-containing polymer. For instance, epoxy compounds, polyols, organic phosphites, substituted dihydropyridines, 1,3-diketones or combinations of these compounds are used.
At the present time, there are no highly effective costabilizers for primary stabilizers based on polymers. Therefore, there remains a need for substances or mixtures of substances which enhance or reinforce the heat-stabilizing action of polymeric primary stabilizers.
Accordingly, one object of this invention is to provide costabilizers which enhance the heat-stabilizing action of stabilizers.
It is another object to provide costabilizers which enhance the heat-stabilizing action of primary polymeric stabilizers.
It is another object to provide costabilizers which enhance the heat-stabilizing action of stabilizers used to stabilize halogen-containing polymers.
It is another object to provide novel stabilizer mixtures which stabilize halogen-containing polymers to the action of heat.
It is another object to provide novel stabilized thermoplastic molding compositions which contain a costabilizer which enhances the heat-stabilizing action of stabilizers.
It is another object to provide novel stabilized thermoplastic molding compositions which contain a costabilizer which enhances the heat-stabilizing action of primary polymeric stabilizers.
It is another object to provide novel stabilized thermoplastic molding compositions based on halogen-containing polymers which contain a stabilizer and a costabilizer which enhances the heat stabilizing action of the stabilizer.
These and other objects which will become apparent during the following detailed description have been achieved by stabilized molding compositions based on chlorine-containing polymers, which contain one or more compounds of zinc of the formula (I)
R.sup.1 O--Zn--OR.sup.2 (I)
in which R1 and R2 may be identical or different and represent straight-chain or branched, unsubstituted or optionally hydroxyl-substituted aliphatic acyl groups having 8 to 21 carbon atoms or aryl groups which are optionally substituted by alkyl groups having 1 to 22 carbon atoms and additionally at least one polymeric primary stabilizer from the group of polyoxazolines of the formula ##STR1## in which each occurrence of R3 can be different and is, independently, a straight-chain or branched alkyl group having 1 to 22 carbon atoms or a substituted or unsubstituted cycloalkyl or aryl group, preferably an alkyl group having 1 to 12 carbon atoms, while n represents an integer of from 10 to 10,000; and
at least two primary-stabilizer-supporting compounds of the formulae III, V or VI and, optionally, in addition a substance according to formula IV ##STR2## and a copolymer (V) composed of ##STR3## in which, in the case of the compound of formula (III), R4 denotes C9 -C22 -alkyl or C9 -C22 -alkenyl, cyclohexyl, phenyl or substituted phenyl; the formula (IV) is a polyfunctional linear and/or branched organic compound having 4 to 20 carbon atoms in which the functional group is understood to be the hydroxyl group; in the case of the compound of the formula (V), which is synthesized from the compounds of the formula (Va) and (Vb), R8 is a straight-chain or branched alkyl group having from 1 to 20 carbon atoms, a cyclic and/or alkyl-substituted cyclic alkyl group having from 5 to 10 carbon atoms, a straight-chain or branched alkenyl group having from 3 to 18 carbon atoms, an alkyl-, halogeno- or hydroxyl-substituted aryl group, a straight-chain or branched alkoxy group having from 1 to 20 carbon atoms, a straight-chain or branched alkylcarbonyl group having from 1 to 20 carbon atoms or a cyano group;
X is a straight-chain or branched alkylene group having from 1 to 20 carbon atoms, a cyclic and/or alkyl-substituted cyclic alkylene group having from 5 to 10 carbon atoms, a straight-chain or branched alkenylene group having from 3 to 18 carbon atoms, an alkyl-, halogeno-, cyano- or hydroxyl-substituted arylene group, a straight-chain or branched alkyleneoxy group having from 1 to 20 carbon atoms, a straight-chain or branched alkylenecarbonyl group having from 1 to 20 carbon atoms; and in the case of the compound of the formula (VI), R9 is methyl or phenyl, R10 is hydrogen, cyano, C2 -C10 -alkylcarbonyl, C7 -C10 -arylcarbonyl, phenylaminocarbonyl, m-hydroxyphenylaminocarbonyl, α-hydroxyethyl or carboxyl which has been esterified with a C1 -C18 -alcohol, C6 -C8 -cycloalkanol, C5 -C19 -aralkanol, C2 -C20 -alkanediol, C4 -C20 -thioalkanediol or pentaerythritol, and R11 is methyl, phenyl or (C1 -C19 -alkoxy)methyl.
A more complete appreciation of the invention and many of the attendant advantages thereof will be readily obtained as the same become better understood by reference to the following detailed description when considered in connection with the accompanying drawings, wherein:
FIGS. 1, 3 and 5 graphically illustrate the heat-stabilizing effect of various stabilizers in various thermoplastic molding compositions by plotting the Yellowness Index (YI) as a function of the time of heat stress, for the stabilizers: Zn/Ca (.), Zn/PC (+), Zn/PC/TMP/DHP (*) and Zn/PC/TMP/DHP/Py (□);
FIGS. 2, 4 and 6 graphically illustrate the heat-stabilizing effect of various stabilizers in various thermoplastic molding compositions by plotting the Yellowness Index (YI) as a function of the time of heat stress, for the stabilizers: Zn/PC/TMP/DHP (*), Zn/PC/TMP/DHP/Py (□), Zn/PC/TMP/DHP/Cop (·) and Zn/PC/TMP/DHP/Py/Cop (-);
FIGS. 7, 11 and 13 graphically illustrate the heat-stabilizing effect of various stabilizers in various thermoplastic molding compositions by plotting the Yellowness Index (YI) as a function of the time of heat stress, for the stabilizers: Zn/Ca( ), Zn/PX (+), Zn/PX/TMP/DHP (*), and Zn/PX/TMP/DHP/Py (□);
FIGS. 8, 10, 12, 14 and 16 graphically illustrate the heat-stabilizing effect of various stabilizers in various thermoplastic molding compositions by plotting the Yellowness Index (YI) as a function of the time of heat stress, for the stabilizers: Zn/PX/TMP/DHP (*), Zn/PX/TMP/DHP/Py (□), Zn/PX/TMP/DHP/Cop (·), and Zn/PX/TMP/DHP/Py/Cop (-);
FIG. 9 graphically illustrates the heat-stabilizing effect of various stabilizers in a thermoplastic molding composition by plotting the Yellowness Index (YI) as a function of the time of heat stress, for the stabilizers: blank (·), Zn/PX (+), Zn/PX/TMP/DHP (*), and Zn/PX/TMP/DHP/Py (□); and
FIG. 15 graphically illustrates the heat-stabilizing effect of various stabilizers in a thermoplastic molding composition by plotting the Yellowness Index (YI) as a function of the time of heat stress, for the stabilizers: ZnOct/CaBeh/Rhod (·), Zn/PX (+), Zn/PX/TMP/DHP (*), and Zn/PX/TMP/DHP/Py (□).
The chlorine-containing polymers are preferably vinyl chloride homopolymers or vinyl chloride copolymers. Preference is furthermore given to suspension polymers and mass polymers and also to emulsion polymers. Suitable comonomers for the copolymers are for example: vinyl acetate, vinylidene chloride, trans-dichloroethene, ethylene, propylene, butylene, maleic acid, acrylic acid, fumaric acid and itaconic acid. Other suitable chlorine-containing polymers are post-chlorinated PVC and chlorinated polyolefins, and also graft copolymers of PVC with ethylene-vinyl acetate (EVA), acrylonitrile-butadienestyrene (ABS) and methacrylate-butadiene-styrene (MBS).
The invention also provides the use of stabilizer systems composed of at least one zinc compound and characterized in that they contain one or more compounds of zinc of the formula
R.sup.1 O--Zn--OR.sup.2 (I),
in which R1 and R2 may be identical or different and represent straight-chain or branched, optionally hydroxyl-substituted aliphatic acyl groups having 8 to 21 carbon atoms or aryl groups which are optionally substituted by alkyl groups having 1 to 22 carbon atoms. The C8 -C21 -carboxylic acids are for example benzoic acid, p-tert-butylbenzoic acid or aliphatic carboxylic acids, in particular octanoic acid, dodecanoic acid, stearic acid or oleic acid.
Preferred examples of zinc compounds are zinc soaps of fatty acids having 8 to 36, preferably 8 to 22 carbon atoms. Suitable examples of these are caprylates, caprates, laurates, myristates, palmitates, stearates and behenates. It is also possible to use the salts of branched fatty acids such as 2-ethylhexanoic acid, 2-octyldecanoic acid or tetradecyloctadecanoic acid or hydroxy-fatty acids such as 9(10)-hydroxystearic acid or 9,10-dihydroxystearic acid. The zinc soaps may be composed of the salts of individual fatty acids or from fatty acid mixtures such as are obtained from natural fats. Suitable salts of aromatic carboxylic acids are in particular the zinc salts of benzoic acid and of substituted benzoic esters, in particular of alkylsubstituted benzoic acid. Suitable phenolates are: methylphenolates, tert-butylphenolates, nonylphenolates, dodecylphenolates or naphthenates of zinc.
Particularly relevant are chlorine-containing polymers which contain a compound of the formula (I) and additionally contain at least one polymeric primary stabilizer from the group of polyoxazolines of the formula: ##STR4## in which each occurrence of R3 may be different and is, independently, a straight-chain or branched alkyl group having 1 to 22 carbon atoms or a substituted or unsubstituted cycloalkyl or aryl group, preferably an alkyl group having 1 to 12-carbon atoms, while n represents an integer of from 10 to 10,000 (cf. DE-C-0,253,985). Examples of compounds of the formula II are polymethyloxazoline, polyethyloxazoline, poly-n-propyloxazoline, polyisopropyloxazoline, polyundecyloxazoline and polyphenyloxazoline. Other primary stabilizers which can be used are copolymers of two different alkyl- or aryl-oxazolines each being present in a proportion of between 5% and 95%. It is also possible to use terpolymers of three different oxazolines, each being present in a proportion of 5 to 95%.
Other highly suitable materials are those stabilized molding compositions which, in addition to the above-mentioned primary stabilizers (I) and (II), contain compounds of tin, lead or antimony or combinations of compounds of cadmium, barium, calcium and zinc and also the primary-stabilizer-supporting costabilizer combinations of compounds of the formulae: ##STR5## and a copolymer (V) composed of ##STR6## in which, in the case of the compound of formula (III), R4 is C9 -C22 -alkyl or C9 -C22 -alkenyl, cyclohexyl, phenyl or substituted phenyl, such as chlorophenyl, anisyl or tolyl. Preference is given to the use of dihydropyridines of the formula (III) in which R4 is C9 -C14 -alkyl (cf. DE-B-2,844,130).
The formula (IV) is a polyfunctional linear and/or branched organic compound having 4 to 20 carbon atoms in which the function is understood to be the hydroxyl group. Preference is given to the use of compounds of the formula (IV) in which R5 and R7 are hydrogen and R6 denotes hydrogen, methyl, ethyl and propyl; a particular example is 2,2-bis(hydroxymethyl)-1-butanol (see, e.g., EP-A-0,315,793).
The compound of the formula (V) is synthesized from compounds of the formula (Va) and (Vb) in which R8 is a straight-chain or branched alkyl group having from 1 to 20 carbon atoms, including, e.g., methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, hexyl, isohexyl, heptyl, isoheptyl, octyl, isooctyl, nonyl, isononyl, decyl, isodecyl, dodecyl, isododecyl, tridecyl, tetradecyl, hexadecyl, octadecyl or arachinyl; or a cyclic or alkyl-substituted cyclic alkyl group having from 5-to 20 carbon atoms, including, e.g., cyclopentyl, cyclohexyl, cycloheptyl, cyclcooctyl, cyclononyl, cyclodecyl, cyclododecyl, cyclotridecyl, cyclotetradecyl, cyclohexadecyl, cyclooctadecyl or cyclcoarachinyl.
R8 may furthermore be a straight-chain or branched alkenyl group having from 3 to 18 carbon atoms including, e.g., propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, dodecenyl, tetradecenyl, hexadecenyl or octadecenyl.
Furthermore, R8 may also represent alkyl-, halogeno-, or hydroxyl-substituted or unsubstituted aryl, such as for example, phenyl, o-tolyl, m-tolyl, p-tolyl, p-tert-butylphenyl, p-nonylphenyl, p-dodecylphenyl, o-hydroxyphenyl, m-hydroxyphenyl, p-hydroxyphenyl, o-chlorophenyl, m-chlorophenyl or p-chlorophenyl.
R8 may also be a straight-chain or branched alkoxy group having from 1 to 20 carbon atom, including, e.g., methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, pentyloxy, isopentyloxy, hexyloxy, isohexyloxy, heptyloxy, isoheptyloxy, octyloxy, isooctyloxy, nonyloxy, isononyloxy, decyloxy, isodecyloxy, dodecyloxy, isododecyloxy, tridecyloxy, tetradecyloxy, hexadecyloxy, octadecyloxy or arachinyloxy; or cyano; or a straight-chain or branched alkylcarbonyl group having from 1 to 20 carbon atoms, including, e.g., methyl-, ethyl-, propyl-, isopropyl-, butyl-, isobutyl-, pentyl-, isopentyl-, hexyl-, isohexyl-, heptyl-, isoheptyl-, octyl-, isooctyl-, nonyl-, isononyl-, decyl-, isodecyl-, dodecyl-, isododecyl-, tridecyl--, tetradecyl-, hexadecyl-, octadecyl- or arachinyl-carbonyl.
X may be a straight-chain or branched alkylene group having from 1 to 20 carbon atoms, including, e.g., methylene, ethylene, propylene, isopropylene, butylene, isobutylene, pentylene, isopentylene, hexylene, isohexylene, heptylene, isoheptylene, octylene, isooctylene, nonylene, isononylene, decylene, isodecylene, dodecylene, isododecylene, tridecylene, tetradecylene, hexadecylene, octadecylene or arachinylene; or a cyclic or alkyl-substituted cycloalkylene group having 5 to 10 carbon atoms, including, e.g., cyclopentylene, cyclohexylene, cycloheptylene, cyclooctylene, cyclononylene, or cyclodecylene.
Moreover, X may also be an alkenylene group having from 3 to 18 carbon atoms, including, e.g., ethenylene, propenylene, butenylene, pentenylene, hexenylene, heptenylene, octenylene, nonenylene, decenylene, dodecenylene, tetradecenylene, hexadecenylene or octadecenylene.
Furthermore, X may also represent an alkyl-, halogen-, cyano, or hydroxyl-substituted or unsubstituted arylene, such as, for example, phenylene, o-tolylene, o-nonylphenylene, o-dodecylphenylene, o-hydroxyphenylene, o-chlorophenylene or o-cyanophenylene.
X may also be a straight chain or branched alkyleneoxy group having from 1 to 20 carbon atoms, including, e.g., methyleneoxy, ethyleneoxy, propyleneoxy, isopropyleneoxy, butyleneoxy, isobutyleneoxy, pentyleneoxy, isopentyleneoxy, hexyleneoxy, isohexyleneoxy, heptyleneoxy, isoheptyleneoxy, octyleneoxy, isooctyleneoxy, nonyleneoxy, isononyleneoxy, decyleneoxy, isodecyleneoxy, dodecyleneoxy, isododecyleneoxy, tridecyleneoxy, tetradecyleneoxy, hexadecyleneoxy, octadecyleneoxy or archinyleneoxy.
X may also be a straight-chain or branched alkylenecarbonyl group having from 1 to 20 carbon atoms, including, e.g., ethylene-, propylene-, isopropylene-, butylene-, isobutylene-, pentylene-, isopentylene-, hexylene-, isohexylene-, heptylene-, isoheptylene-, octylene-, isooctylene-, nonylene-, isononylene-, decylene-, isodecylene-, dodecylene-, isododecylene-, tridecylene-, tetradecylene-, hexadecylene-, octadecylene- or arachinylene-carbonyl.
Preference is given to the use of compounds of the formulae (Va) and (Vb) in which R8 is methyl, ethyl or propyl and in which X is ethylene, trimethylene, tetramethylene or phenylene.
The preparation of the costabilizers V may be carried out by reacting the compounds (Va) and (Vb) in a mole ratio of from 90:10 to 99:1, preferably from 94:6 to 99:1, especially preferably in a ratio of Va:Vb greater than about 95:5, in particular in about 97.5 to 2.5, mole% in ethylbenzene (containing about 95 ppm of water) with catalytic amounts (0.5 to 1.5 mole%, in particular 0.9 mole%) of methyl 4-toluenesulphonate employing a reaction time of about 12 to 15 minutes at 133° C. and a post-polymerization time of 60 minutes at 133° C. A crosslinked copolymer (V) is obtained in yields of >95%.
In the case of the compound of the formula (VI), R9 is methyl or phenyl, R10 is hydrogen, cyano, C2 -C19 -alkylcarbonyl, C7 -C10 -arylcarbonyl, phenylaminocarbonyl, m-hydroxyphenylaminocarbonyl, α-hydroxyethyl, or carboxyl esterified with a C1 -C18 -alcohol, C5 -C8 -cycloalkanol, C5 -C19 -aralkanol, C2 -C20 -alkanediol, C4 -C20 -thioalkanediol or pentaerythritol, and R11 is methyl, phenyl or (C1 -C19 -alkoxy) methyl.
R10 as C2 -C19 -alkylcarbonyl is in particular propionyl, butyryl, lauroyl or particularly acetyl, as C7 -C10 -arylcarbonyl is optionally substituted benzoyl, in particular benzoyl itself, and, as esterified carboxyl, is one which has been esterified with C1 -C18 -alkanol such as for example, methanol, ethanol, n-octanol or lauryl alcohol, C6 -C19 -aralkanol such as for example, benzyl alcohol or furfuryl alcohol, C5 -C8 -cycloalkanol such as for example, cyclohexanol, C2 -C20 -alkanediol such as ethylene glycol or 1,2-butylene glycol, C4 -C20 -thioalkanediol such as for example, 3-thio-1,5-dihydroxypentane, or pentaerythritol.
R11 as C1 -C18 -alkoxymethyl is in particular methoxymethyl or ethoxymethyl.
Preference is given to the use of the pyrroles, 2-methyl-3-ethoxycarbonyl-4-phenylpyrrole and 2-methyl-3-methoxycarbonyl-4-phenylpyrrole.
The pyrroles may be prepared by a plurality of methods (see, e.g., Houben-Weyl, Methoden der organischen Chemie, Nitrogen Compounds II, volume 11/1).
One method of preparation is to condense α-chloroketones and β-ketoesters under the action of NH3.
The stabilized molding compositions contain the compounds of the formula I and II advantageously in amounts in each case of 0.02 to 2.0 percent by weight, in particular in amounts of 0.05 to 1.0 percent by weight, based on the weight of the chlorine-containing polymer.
The stabilized molding compositions contain the compounds of the formulae III to VI advantageously in amounts from 0 to 2.0 percent by weight, preferably, in the case of compounds of the formula III, in amounts from 0.05 to 0.1 percent by weight, in the case of compounds of the formula IV in amounts from 0.02 to 1.0 percent by weight, in the case of compounds of the formula VI in amounts from 0.05 to 1.0 percent by weight, and in the case of compounds of the formula V advantageously in amounts from 0.001 to 2.0, in particular 0.01 to 0.05 percent by weight, based on the weight of the chlorine-containing polymer.
The costabilizers are used as follows:
At least two representatives from the substance categories III, V or VI must be used; in addition, a compound of the formula IV may be added.
It is possible to use commercially available costabilizers in conjunction with the listed costabilizers.
Suitable prior-art phosphites are phosphites of the general formulae VII and VIII ##STR7## in which R12, R13 and R14 are identical or different and are C6 -C18 -alkyl, a phenyl group which may be unsubstituted or substituted with C1 -C9 -alkyl or C1 -C9 -alkoxy, or C5 -C7 -cycloalkyl, and in which R15 is C5 -C18 -alkyl.
If R12, R13, R14 and R15 denote C6 -C18 -alkyl, this is for example n-hexyl, n-octyl, n-nonyl, decyl, dodecyl, tetradecyl, hexadecyl or octadecyl. Preference is given to alkyl groups having 8 to 12 carbon atoms.
R12, R13 and R14, as substituted phenyl, are for example tolyl, ethylphenyl, xylyl, nonyl, cumyl, cresyl, 4-methoxyphenyl, 2,4-dimethoxyphenyl, ethoxyphenyl, butoxyphenyl, p-n-octylphenyl or p-n-nonylphenyl.
Most particularly suitable phosphites are trioctyl, tridecyl, tridodecyl, tritetradecyl, tristearyl, trioleyl, triphenyl, tricresyl, tris-p-nonylphenyl and tricyclohexyl phosphite, and particular preference is given to the aryl dialkyl phosphites and also to the alkyl diaryl phosphites such as for example, phenyl didecyl phosphite, nonylphenyl didecyl phosphite, (2,4-di-tertbutylphenyl) didodecyl phosphite and (2,6-di-tert-butylphenyl) didodecyl phosphite.
Examples of antioxidants are alkylated monophenols and hydroquinones, hydroxylated thiodiphenyl ethers, 1,4 alkylidene-bis-phenols, benzyl compounds, acylaminophenols, esters or amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid and esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid.
Preferred antioxidants are alkylated monophenols, alkylidene-bisphenols and phenyl-substituted propionic esters, in particular, 2,6-di-tert-butyl-p-cresol, 2,2bis(4'-hydroxyphenyl)propane and n-octadecyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate.
The compounds of the formulae III to VI can also be used with other nitrogen-containing organic stabilizers. Examples of these are cyanamide, dicyandiamide, guanamines such as benzoguanamine, indoles such as phenylindole, pyrazoles (for example as described in GB-B-866,936), ureas and thioureas such as monophenylurea and diphenylthiourea, and aminocrotonic esters; also, β-diketones such as stearylbenzoylmethane, and polyols such as pentaerythritol.
It is observed, with the stabilized molding compositions according to the invention based on polymers of vinyl chloride which contain compounds of the formulae III to VI as costabilizers, that these compounds enhance the stabilizing action of a primary stabilizer mixture of zinc compounds and polymers from the group of polyoxazolines to an extent which could not have been foreseen. The positive effect of these costabilizers is seen as an improvement in the initial color and as a prolongation of the ultimate stability of the halogen-containing polymer. Until now, it has not been possible to achieve this effect by the addition of known costabilizer mixtures.
It is possible to prepare the stabilized molding compositions according to the invention by conventional methods, for example by simple mechanical mixing of the components in conventional mixers. This mixing operation may be used to incorporate other conventional processing auxiliaries, such as for example, lubricants (montan waxes or polyol partial esters), plasticizers, fillers, light stabilizers, pigments or other costabilizers, such as for example, epoxidized fatty acid esters.
It is possible to achieve a homogeneous distribution of the stabilizers in PVC, for example, with the aid of a two-roll mill at 150° to 200° C.
Other features of the invention will become apparent in the course of the following descriptions of exemplary embodiments which are given for illustration of the invention and are not intended to be limiting thereof.
The action of various stabilizer combinations was tested by determining the static heat stability of a milled sheet. For this purpose, the stabilizer combinations and, optionally, plasticizers and processing auxiliaries were mixed with polyvinyl chloride for 30 seconds in a laboratory mill and then processed on a two-roll mill at a roll temperature of 170° C., with co-rotation, over the course of 5 minutes to form 1 mm thick milled sheets. Strips of dimensions 14×250 mm were cut from the milled sheets and these strips were then subjected to heat stress in a -special oven (Metrastat, type Sigma) at 180° C. Under the test conditions, the test strips were continuously discharged from the heating zone, and the effect of the stabilizers on the color variation was determined.
The color variations were assessed objectively and in comparison with each other by determining the yellowness indices (YI; ASTM Method E 313-73) using a colorimeter (LabScan 5100 plus) from Dr. Slevogt & Co. and plotting yellowness indices against the duration of heat stress. High YI values indicate strong discoloration and thus low stability.
The following stabilizers were used:
Zn=Zinc stearate
ZnOct=Zinc octoate
Ca=Calcium stearate
CaBeh=Calcium behenate
Ba=Barium stearate
Rhod=Benzoylstearoylmethane
PX=Polyethyloxazoline
Cop=Copolymer of ethyloxazoline and tetramethylenebisoxazoline (mole ratio 97,5:2,5)
PC=Copolymer of methyloxazoline and isopropyloxazoline
TMP=Trimethylolpropane
DHP=Dihydro-dimethyl-bis(dodecylcarbonyl)pyridine
Py=Methyl-phenyl-ethyoxycarbonylpyrrole
Formulations were prepared from the following ingredients (parts=parts by weight):
100 parts of suspension-polyvinyl chloride (K-value 70; VESTOLIT S 7054; Huls AG, Marl, West Germany)
30 parts of dioctyl phthalate (VESTINOL AH; Huls AG, Marl, West Germany)
0.3 part of montan wax
100 parts of suspension-polyvinyl chloride (K-value 70; VESTOLIT S 7054; Huls AG, Marl, West Germany)
30 parts of dioctyl phthalate (VESTINOL AH; Huls AG, Marl, West Germany)
0.3 part of zinc stearate
0.6 part of barium stearate
100 parts of suspension-polyvinyl chloride (K-value 70; VESTOLIT S 7054; Huls AG, Marl, West Germany)
1.0 part of stearic acid
100 parts of suspension-polyvinyl chloride (K-value 60; VESTOLIT S 6058; Huls AG, Marl, West Germany)
1.0 part of stearic acid
100 parts of mass-polyvinyl chloride (K-value 58; VESTOLIT M 5867; Huls AG, Marl, West Germany)
5.0 parts of epoxidized soy bean oil (Reoplast 39, Ciba-Geigy AG, Bensheim, West Germany)
The polyvinyl chloride molding compositions were prepared by adding one of the stabilizers from the given tables to one of the formulations A to E, and these mixes were processed in the manner described above to form test strips. The results are presented in Examples 1-16 and FIGS. 1-16.
A stabilizer mixture from Table 1 was mixed with the indicated formulation, and the results are shown in each example.
TABLE 1
______________________________________
Formulations of the Stabilizers (parts by weight).
Stabilizer mixtures
Zn Ca PC TMP DHP Py Cop
______________________________________
Zn/Ca 0.5 1
Zn/PC 0.2 0.2
Zn/PC/TMP 0.2 0.2 0.5
Zn/PC/DHP 0.2 0.2 0.07
Zn/PC/TMP/DHP 0.2 0.2 0.5 0.07
Zn/PC/TMP/DHP/Py
0.2 0.2 0.5 0.07 0.1
Zn/PC/TMP/DHP/Cop
0.2 0.17 0.5 0.07 0.03
Zn/PC/TMP/DHP/Py/
0.2 0.17 0.5 0.07 0.1 0.03
Cop
______________________________________
100 parts by wt. of VESTOLIT S 7054
1.0 part by wt. of stearic acid
______________________________________
Heat Stress (min)
Stabilizers 10 15 20 25 30 35 40
______________________________________
Zn/Ca 40 36 39 44 48 55 62
Zn/PC 23 25 28 31 35 59 --
Zn/PC/TMP/DHP 6 8 9 12 16 24 --
Zn/PC/TMP/DHP/Py
8 9 11 14 19 28 46
______________________________________
These results are presented graphically in FIG. 1.
100 parts by wt. of VESTOLIT S 7054
1.0 part by wt. of stearic acid
______________________________________
Heat Stress (min)
Stabilizers 10 15 20 25 30 35 40
______________________________________
Zn/PC/TMP/DHP 6 8 9 12 16 24 --
Zn/PC/TMP/DHP/Py
8 9 11 14 19 28 46
Zn/PC/TMP/DHP/Cop
6 7 10 13 17 31 --
Zn/PC/TMP/DHP/Py/Cop
8 8 11 15 18 23 62
______________________________________
These results are presented graphically in FIG. 2.
100 parts by wt. of VESTOLIT S 6058
1.0 part by wt. of stearic acid
______________________________________
Heat Stress (min)
Stabilizers 10 15 20 25 30 35
______________________________________
Zn/Ca 41 40 43 46 54 63
Zn/PC 19 22 25 29 33 59
Zn/PC/TMP/DHP 6 8 9 11 54 75
Zn/PC/TMP/DHP/Py
8 9 9 11 12 84
______________________________________
These results are presented graphically in FIG. 3.
100 parts by wt. of VESTOLIT S 6058
1.0 part by wt. of stearic acid
______________________________________
Heat Stress (min)
Stabilizers 10 15 20 25 30 35
______________________________________
Zn/PC/TMP/DHP 6 8 9 11 54 75
Zn/PC/TMP/DHP/Py 8 9 9 11 12 84
Zn/PC/TMP/DHP/Cop
7 8 10 12 16 73
Zn/PC/TMP/DHP/Py/Cop
7 9 10 12 17 63
______________________________________
These results are presented graphically in FIG. 4.
100 parts by wt. of VESTOLIT S 7054
30 parts by wt. of VESTINOL AH
0.3 parts by wt. of Montan wax
______________________________________
Heat Stress (min)
Stabilizers 10 15 20 25 30 35 40 45
______________________________________
Zn/Ca 13 14 15 15 12 14 30 84
Zn/PC 6 6 7 8 7 11 61 95
Zn/PC/TMP/DHP 4 4 4 4 5 6 18 93
Zn/PC/TMP/DHP/Py
4 4 4 5 6 7 12 57
______________________________________
These results are presented graphically in FIG. 5.
100 parts by wt. of VESTOLIT S 7054
30 parts by wt. of VESTINOL AH
0.3 parts by wt. of Montan wax
______________________________________
Heat Stress (min)
Stabilizers 10 15 20 25 30 35 40 45
______________________________________
Zn/PC/TMP/DHP 4 4 4 4 5 6 18 93
Zn/PC/TMP/DHP/Py 4 4 4 5 6 7 12 57
Zn/PC/TMP/DHP/Cop
4 4 4 4 5 7 23 95
Zn/PC/TMP/DHP/Py/Cop
4 4 4 5 5 6 9 21
______________________________________
These results are presented graphically in FIG. 6.
A stabilizer mixture from Table 2 was mixed with the indicated formulation, and the results are shown in each example.
TABLE 2
______________________________________
Formulations of Stabilizers (parts by weight).
Zn Ca PX TMP DHP Py Cop
______________________________________
Blank 0
Zn/Ca 0.5 1
Zn/PX 0.2 0.2
Zn/PX/TMP 0.2 0.2 0.5
Zn/PX/DHP 0.2 0.2 0.07
Zn/PX/TMP/DHP 0.2 0.2 0.5 0.07
Zn/PX/TMP/DHP/Py
0.2 0.2 0.5 0.07 0.1
Zn/PX/TMP/DHP/Cop
0.2 0.17 0.5 0.07 0.03
Zn/PX/TMP/DHP/Py/
0.2 0.17 0.5 0.07 0.1 0.03
Cop
______________________________________
100 parts by wt. of VESTOLIT S 6058
1.0 part by wt. of stearic acid
______________________________________
Heat Stress (min)
Stabilizers 10 15 20 25 30 35
______________________________________
Zn/Ca 43 45 46 51 56 66
Zn/PX 23 25 29 32 38 65
Zn/PX/TMP/DHP 7 9 10 12 15 68
Zn/PX/TMP/DHP/Py
9 10 11 14 20 69
______________________________________
These results are presented graphically in FIG. 7.
100 parts by wt. of VESTOLIT S 6058
1.0 part by wt. of stearic acid
______________________________________
Heat Stress (min)
Stabilizers 10 15 20 25 30 35
______________________________________
Zn/PX/TMP/DHP 7 9 10 12 15 68
Zn/PX/TMP/DHP/Py
9 10 11 14 20 69
Zn/PX/TMP/DHP/Cop
7 8 10 13 17 48
Zn/PX/TMP/DHP/Py/Cop
7 9 10 12 15 80
______________________________________
These results are presented graphically in FIG. 8.
100 parts by wt. of VESTOLIT S 7054
30 parts by wt. of VESTINOL AH
0.3 parts by wt. of zinc stearate
0.6 parts by weight of barium stearate
__________________________________________________________________________
Heat Stress (min)
Stabilizers 10
15
20
25
30
35
40
45
50
55
60
65
70
75
__________________________________________________________________________
Blank 13
13
15
12
10
9
23
83
--
--
--
--
--
--
Zn/Px 11
12
13
15
14
13
14
18
32
66
93
--
--
--
Zn/Px/TMP/DHP
6
7
7
9
12
16
20
17
16
25
51
80
--
--
Zn/Px/TMP/DHP/Py
7
7
7
9
12
15
18
20
24
29
34
43
61
84
__________________________________________________________________________
These results are presented graphically in FIG. 9.
100 parts by wt. of VESTOLIT S 7054
30 parts by wt. of VESTINOL AH
0.3 part by wt. of zinc stearate
0.6 part by weight of barium stearate
__________________________________________________________________________
Heat Stress (min)
Stabilizers 10
15
20
25
30
35
40
45
50
55
60
65
70
__________________________________________________________________________
Zn/PX/TMP/DHP 6 7 7 9
12
16
20
17
16
25
51
80
--
Zn/Px/TMP/DHP/Py
7 7 7 9
12
15
18
20
24
29
34
43
61
Zn/PX/TMP/DHP/Cop
7 7 8 10
13
17
19
16
18
29
60
89
--
Zn/PX/TMP/DHP/Py/Cop
6 6 7 9
12
15
18
20
25
30
38
46
73
__________________________________________________________________________
These results are presented graphically in FIG. 10.
100 parts by wt. of VESTOLIT S 7054
1.0 part by wt. of stearic acid
______________________________________
Heat Stress (min)
Stabilizers 10 15 20 25 30 35 40 45
______________________________________
Zn/Ca 40 42 45 49 55 61 61 --
Zn/PX 22 25 29 34 37 61 -- --
Zn/PX/TMP/DHP 7 9 10 14 21 41 -- --
Zn/PX/TMP/DHP/Py
7 7 9 12 16 21 27 49
______________________________________
These results are presented graphically in FIG. 11.
100 parts by wt. of VESTOLIT S 7054
1.0 part by wt. of stearic acid
______________________________________
Heat Stress (min)
Stabilizers 10 15 20 25 30 35 40 45
______________________________________
Zn/PX/TMP/DHP 7 9 10 14 21 41 -- --
Zn/PX/TMP/DHP/Py 7 7 9 12 16 21 27 49
Zn/PX/TMP/DHP/Cop
6 7 8 11 15 21 42 --
Zn/PX/TMP/DHP/Py/Cop
8 9 11 14 20 28 73 --
______________________________________
These results are presented graphically in FIG. 12.
100 parts by wt. of VESTOLIT S 7054
30 parts by wt. of VESTINOL AH
0.3 parts by wt. of Montan wax
______________________________________
Heat Stress (min)
Stabilizers 10 15 20 25 30 35 40 45 50
______________________________________
Zn/Ca 12 12 13 15 12 12 20 61 90
Zn/PX 6 6 7 8 9 9 40 91 95
Zn/PX/TMP/DHP 4 4 4 5 5 7 24 93 95
Zn/PX/TMP/DHP/Py
4 4 5 5 7 7 8 19 81
______________________________________
These results are presented graphically in FIG. 13.
100 parts by wt. of VESTOLIT S 7054
30 parts by wt. of VESTINOL AH
0.3 part by wt. of Montan wax
______________________________________
Heat Stress (min)
Stabilizers 10 15 20 25 30 35 40 45 50
______________________________________
Zn/PX/TMP/DHP 4 4 4 5 5 7 24 93 95
Zn/PX/TMP/DHP/Py
4 4 5 5 7 7 8 19 81
Zn/PX/TMP/DHP/Cop
4 4 4 4 5 5 11 82 89
Zn/PX/TMP/DHP/Py/
4 4 4 4 5 5 6 10 61
Cop
______________________________________
These results are presented graphically in FIG. 14.
100 parts by wt. of VESTOLIT M 5867
5.0 parts by wt. of Reoplast 39
__________________________________________________________________________
Heat Stress (min)
Stabilizers 10
15
20
25
30
35
40
45
50
55
60
65
70
__________________________________________________________________________
ZnOct/CaBeh/Rhod*
7 7 8 9
12
18
26
35
47
62
--
--
--
Zn/PX 8 8 9 11
14
18
28
43
57
65
76
81
91
Zn/Px/TMP/DHP
3 3 3 4
4
6
11
20
32
43
52
65
79
Zn/Px/TMP/DHP/Py
4 4 4 5
5
7
12
19
29
40
48
58
69
__________________________________________________________________________
*Comparative sample: 0.075 parts of ZnOct/0.35 parts of CaBeh/0.3 parts o
Rhod.
These results are presented graphically in FIG. 15.
100 parts by wt. of VESTOLIT M 5867
5.0 parts by wt. of Reoplast 39
__________________________________________________________________________
Heat Stress (min)
Stabilizers 10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
__________________________________________________________________________
Zn/PX/TMP/DHP
3 3 3 4 4 6 11
20
32
43
52
65
79
82
--
Zn/Px/TMP/DHP/Py
4 4 4 5 5 7 12
19
29
40
48
58
69
83
--
Zn/PX/TMP/DHP/Cop
3 3 3 4 4 7 13
23
34
43
52
63
76
--
--
Zn/PX/TMP/DHP/Py/
4 4 4 4 6 7 11
19
29
38
48
57
65
74
86
Cop
__________________________________________________________________________
These results are presented graphically in FIG. 16.
Obviously, numerous modifications and variations of the present invention are possible in light of the above teachings. It is therefore to be understood that, within the scope of the appended claims, the invention may be practiced otherwise than as specifically described herein.
Claims (10)
1. A stabilized thermoplastic molding composition comprising,
(a) a halogen-containing polymer;
(b) one or more compounds of zinc of formula (I)
R.sup.1 O--Zn--OR.sup.2 (I)
wherein R1 and R2 are identical or different and represent a straight-chain or branched, hydroxyl-substituted or unsubstituted aliphatic acyl group having from 8 to 21 carbon atoms or an aryl group which is optionally substituted with alkyl groups having 1 to 22 carbon atoms;
(c) at least one polymeric primary stabilizer selected from the group of polyoxazolines of formula (II) ##STR8## wherein each occurrence of R3 can be different and is, independently, a straight-chain or branched alkyl group having 1 to 22 carbon atoms or substituted or unsubstituted cycloalkyl or aryl group, and n represents an integer of from 10 to 10,000; and
(d) at least two primary-stabilizer-supporting compounds of the formulae (III), (V) or (VI): ##STR9## wherein (V) is a copolymer of ##STR10## wherein in formula (III), R4 is C9 -C22 -alkyl or C9 -C22 -alkenyl, cyclohexyl, phenyl or substituted phenyl;
in formulae (Va) or (Vb), R8 is a straight-chain or branched alkyl group having from 1 to 20 carbon atoms, a cyclic and/or alkyl-substituted cyclic alkyl group having from 5 to 10 carbon atoms, a straight-chain or branched alkenyl group having from 3 to 18 carbon atoms, an alkyl-, halogeno- or hydroxyl-substituted aryl group, a straight-chain or branched alkoxy group having from 1 to 20 carbon atoms, a straight-chain or branched alkylcarbonyl group having from 1 to 20 carbon atoms or a cyano group;
X is a straight-chain or branched alkylene group having from 1 to 20 carbon atoms, a cyclic and/or alkyl-substituted cyclic alkylene group having from 5 to 10 carbon atoms, a straight-chain or branched alkenylene group having from 3 to 18 carbon atoms, an alkyl-, halogeno-, cyano- or hydroxyl-substituted arylene group, a straight-chain or branched alkyleneoxy group having from 1 to 20 carbon atoms, a straight-chain or branched alkylenecarbonyl group having from 1 to 20 carbon atoms; and
in formula (VI), R9 is methyl or phenyl, R10 is hydrogen, cyano, C2 -C10 -alkylcarbonyl, C7 -C10 -arylcarbonyl, phenylaminocarbonyl, m-hydroxyphenylaminocarbonyl, α-hydroxyethyl, or carboxyl which has been esterified with a C1 -C18 -alcohol, C6 -C8 -cycloalkanol, C5 -C19 -aralkanol, C2 -C20 -alkanediol, C4 -C20 -thioalkanediol or pentaerythritol, and R11 is methyl, phenyl or (C1 -C19 -alkoxy)methyl.
2. The stabilized molding composition of claim 1, wherein said compounds of formulae (I) and (II) are each present in amounts of 0.02 to 2.0 percent by weight and the compounds of the formulae (III), (V), and (VI) are present in amounts of 0 to 2.0 percent by weight, based on the weight of the chlorine-containing polymer.
3. The stabilized molding composition of claim 1, further comprising a primary stabilizer in the form of a compound of zinc, lead or antimony or a combination of compounds of cadmium, barium, calcium and zinc and an additional costabilizer selected from the group consisting of phosphites, 1,3-diketones, polyols, alkylated phenols, cyanamides, dicyandiamides, guanamines, indoles, pyrazoles, ureas, thioureas, monophenylureas, diphenylthiourea and aminocrotonic esters.
4. The stabilized molding composition of claim 1, further comprising a compound of formula (IV) ##STR11## wherein R5 and R7 are hydrogen and R6 is hydrogen, methyl, ethyl, or propyl.
5. The stabilized molding composition of claim 1, wherein said compound of formula IV is present in an amount of up to 2.0 percent by weight based on the weight of the halogen-containing polymer.
6. The stabilized molding composition of claim 1, wherein R3 is an alkyl group having 1 to 12 carbon atoms.
7. The stabilized molding composition of claim 1, wherein said halogen-containing polymer is polyvinyl chloride.
8. A stabilizer mixture, comprising:
(a) one or more compounds of zinc of formula (I)
R.sup.1 O--Zn--OR.sup.2 (I)
wherein R1 and R2 are identical or different and represent a straight-chain or branched, hydroxyl-substituted or unsubstituted aliphatic acyl group having from 8 to 21 carbon atoms or an aryl group which is optionally substituted with alkyl groups having 1 to 22 carbon atoms;
(b) at least one polymeric primary stabilizer selected from the group of polyoxazolines of formula (II) ##STR12## wherein each occurrence of R3 can be different and is, independently, a straight-chain or branched alkyl group having 1 to 22 carbon atoms or substituted or unsubstituted cycloalkyl or aryl group, and n represents an integer of from to 10,000; and
(c) at least two primary-stabilizer-supporting compounds of the formulae (III), (V) or (VI): ##STR13## wherein (V) is a copolymer of ##STR14## wherein in formula (III), R4 is C9 -C22 -alkyl or C9 -C22 -alkenyl, cyclohexyl, phenyl or substituted phenyl;
in formulae (Va) and (Vb), R8 is a straight-chain or branched alkyl group having from 1 to 20 carbon atoms, a cyclic and/or alkyl-substituted cyclic alkyl group having from 5 to 10 carbon atoms, a straight-chain or branched alkenyl group having from 3 to 18 carbon atoms, an alkyl-, halogen- or hydroxyl-substituted aryl group, a straight-chain or branched alkoxy group having from 1 to 20 carbon atoms, a straight-chain or branched alkylcarbonyl group having from 1 to 20 carbon atoms or a cyano group;
X is a straight-chain or branched alkylene group having from 1 to 20 carbon atoms, a cyclic and/or alkyl-substituted cyclic alkylene group having from 5 to 10 carbon atoms, a straight-chain or branched alkenylene group having from 3 to 18 carbon atoms, an alkyl-, halogeno-, cyano- or hydroxyl-substituted arylene group, a straight-chain or branched alkyleneoxy group having from 1 to 20 carbon atoms, a straight-chain or branched alkylenecarbonyl group having from 1 to 20 carbon atoms; and
in formula (VI), R9 is methyl or phenyl, R10 is hydrogen, cyano, C2 -C10 -alkylcarbonyl, C7 -C10 -arylcarbonyl, phenylaminocarbonyl, m-hydroxyphenylaminocarbonyl, α-hydroxyethyl, or carboxyl which has been esterified with a C1 -C18 -alcohol, C6 -C8 -cycloalkanol, C5 -C19 -aralkanol, C2 -C20 -alkanediol, C4 -C20 -thioalkanediol or pentaerythritol, and R11 is methyl, phenyl or (C1 -C19 -alkoxy)methyl.
9. The stabilizer mixture of claim 8, further comprising a compound of formula (IV) ##STR15## wherein R5 and R7 are hydrogen and R6 is hydrogen, methyl, ethyl, or propyl.
10. The stabilizer mixture of claim 8, wherein R3 is an alkyl group having 1 to 12 carbon atoms.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3932048 | 1989-09-26 | ||
| DE3932048A DE3932048A1 (en) | 1989-09-26 | 1989-09-26 | COSTABILIZERS FOR MOLDS BASED ON VINYL CHLORIDE POLYMERS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US5049602A true US5049602A (en) | 1991-09-17 |
Family
ID=6390192
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US07/589,803 Expired - Fee Related US5049602A (en) | 1989-09-26 | 1990-09-26 | Costabilizers for molding compositions based on polymers of vinyl chloride |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US5049602A (en) |
| EP (1) | EP0419794A1 (en) |
| JP (1) | JPH03122151A (en) |
| CA (1) | CA2026034A1 (en) |
| DD (1) | DD298124A5 (en) |
| DE (1) | DE3932048A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5244949A (en) * | 1990-11-30 | 1993-09-14 | Ciba-Geigy Corporation | Stabilized chlorine-containing polymers |
| FR2811324A1 (en) * | 2000-07-04 | 2002-01-11 | Rhodia Chimie Sa | STABILIZATION OF HALOGENATED POLYMERS BY MEANS OF PYRROLES OR DERIVATIVES AND COMPOSITIONS CONTAINING THEM |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2709667B1 (en) * | 1993-09-08 | 1995-11-10 | Hospal Ag | Formulation of plasticized polyvinyl chloride for stamping containers for bicarbonate solutions, in particular for dialysis. |
| ATE182466T1 (en) * | 1993-07-23 | 1999-08-15 | Hospal Ag | METHOD FOR STABILIZING AND REDUCING THE CO2 PERMEABILITY OF BICARBONATE SOLUTION CONTAINERS MADE OF PLASTICIZED POLYVINYL CHLORIDE |
| AU2001275691A1 (en) * | 2000-07-14 | 2002-01-30 | Akzo Nobel N.V. | Stabilizer compositions comprsing a monomeric dihydropyridine derivative and their use |
| DE10317870A1 (en) * | 2003-04-17 | 2004-11-04 | Crompton Vinyl Additives Gmbh | New stabilizer system for stabilizing halogen-containing polymers |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4267083A (en) * | 1978-05-12 | 1981-05-12 | Rhone-Poulenc Industries | Heat-stabilized vinyl chloride polymers |
| US4369276A (en) * | 1979-06-28 | 1983-01-18 | Ciba-Geigy Corporation | Pyrrole stabilizers for chlorine-containing thermoplastics |
| US4515916A (en) * | 1982-05-18 | 1985-05-07 | Morton Thiokol Inc. | Stabilizers for halogen containing polymers comprising zinc mercaptoesters, basic inorganic alkali or alkaline earth metal compounds and, substituted dihydropyridines |
| US4755549A (en) * | 1986-07-17 | 1988-07-05 | Huels Aktiengesellschaft | Stabilized molding compounds based on polyvinyl chloride or vinyl chloride copolymers and stabilizer system |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU524086B2 (en) * | 1978-12-22 | 1982-09-02 | Sanofi | Stabilization of vinyl resins |
-
1989
- 1989-09-26 DE DE3932048A patent/DE3932048A1/en not_active Withdrawn
-
1990
- 1990-07-25 EP EP90114244A patent/EP0419794A1/en not_active Withdrawn
- 1990-09-24 CA CA002026034A patent/CA2026034A1/en not_active Abandoned
- 1990-09-25 DD DD90344179A patent/DD298124A5/en not_active IP Right Cessation
- 1990-09-26 US US07/589,803 patent/US5049602A/en not_active Expired - Fee Related
- 1990-09-26 JP JP2254389A patent/JPH03122151A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4267083A (en) * | 1978-05-12 | 1981-05-12 | Rhone-Poulenc Industries | Heat-stabilized vinyl chloride polymers |
| US4369276A (en) * | 1979-06-28 | 1983-01-18 | Ciba-Geigy Corporation | Pyrrole stabilizers for chlorine-containing thermoplastics |
| US4515916A (en) * | 1982-05-18 | 1985-05-07 | Morton Thiokol Inc. | Stabilizers for halogen containing polymers comprising zinc mercaptoesters, basic inorganic alkali or alkaline earth metal compounds and, substituted dihydropyridines |
| US4755549A (en) * | 1986-07-17 | 1988-07-05 | Huels Aktiengesellschaft | Stabilized molding compounds based on polyvinyl chloride or vinyl chloride copolymers and stabilizer system |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5244949A (en) * | 1990-11-30 | 1993-09-14 | Ciba-Geigy Corporation | Stabilized chlorine-containing polymers |
| FR2811324A1 (en) * | 2000-07-04 | 2002-01-11 | Rhodia Chimie Sa | STABILIZATION OF HALOGENATED POLYMERS BY MEANS OF PYRROLES OR DERIVATIVES AND COMPOSITIONS CONTAINING THEM |
| WO2002002685A3 (en) * | 2000-07-04 | 2002-03-14 | Rhodia Chimie Sa | Stabilising halogenated polymers with pyrroles or derivatives thereof and compositions containing them |
| US20030187109A1 (en) * | 2000-07-04 | 2003-10-02 | Prud'homme Christian | Stabilising halogenated polymers with pyrroles or derivatives thereof and compositions containing them |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0419794A1 (en) | 1991-04-03 |
| CA2026034A1 (en) | 1991-03-27 |
| DE3932048A1 (en) | 1991-04-04 |
| JPH03122151A (en) | 1991-05-24 |
| DD298124A5 (en) | 1992-02-06 |
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